Glycol esters of phenylphosphonic acid



Patented Aug. 14, 1945 d Arthur-Dock Fon Toy, Chicago, 111., amino: to

linois Viotor Chemical Works. a corporation of n- This invention relatesto the production of phenyl phosphonic acid esters of ethylen andtrimethylene glycols and alkyl substituted ethylene and trimethyleneglycols, and more particularly to the production of such esters by thereaction of phenyl phosphorus oxydichlorlde with ethylene andtrimethyleneslyools and their alkyl substituted products.

In accordance with the present discovery it has been found that ethyleneglycol and trimethylene glycol will react with phenyl phosphorusoxydichloride to produce ring type esters of the fol-.

lowing type formula:

' O-CHI CsHs 0- H and Hi o o-o CQH|{L'\ CH:

Glycols in which there are more than three carbon atoms in a straightchain between the hydroxy groups do not react to give definite estersbut only resinous compositions. Side chain groups, however, may besubstituted without interfering with the ester reaction. For example2,3-butanediol will react to give esters of the type herein described.The type .of glycol employed in the present invention may be designatedby the formula HO(CHY)OH, where a: is 2 or 3 and Y is hydrogen or a sidechain alkyl group.

The reaction of the giycols with phenyl phosphorus oxydichloride isquite vigorous and requires that the temperature be controlled duringthe early stages at a temperature low enough to avoid decompositionwhile in the presence of high concentrations of hydrogen chloride. Thegeneral equation for the reaction is as follows:

maroon nownraon 2H01 mmK Boar where :c is limited to 2 or 3, and Yishydrogen or an alkyl group.

As a typical xample of the process, 58.5 parts of phenyl phosphorusoxydichloride and 19.5 parts (by weight) of ethylene glycol were mixedin a reaction vessel under vacuum while maintaining a temperature of notover about 25 C. After approximately 85 to 95% of the hydrogen chlorideis removed, the heat is raised to distill oi the excess ethylene glycol.The remaining product which is the phenyl-phosphonate of ethylene slycolis then purifled/bydistillation or other suitable means. By distillationa yield of approximately 75% of the ester product was obtained.

This ester has a boiling point of approximately 210 C. at 8-7 pressureand when cooled forms a hygroscopic. white, crystalline solid.

In a similar manner. trimethylene glycol and phenyl phosphorusoxydichloride were reacted to produce the phenylphosphonate oftrimethylene glycol which is a slightly colored oily product having aboiling point of 212-214 C. at 7.5 mm.pres'- sure. The cats: product waobtained in a yield 7 of approximately 67%.

In another example, 28.4 grams (0.315 mole) levo 2,8-butanediolnoon-anon) Ha H:

0 was reacted with 58.5 grams (0.3 mole) phenyl The above type estercompounds are suitable for use as plasticizing and oil addition agents.

The foregoing detailed description has been given for clearness ofunderstanding only, and no unnecessary limitations should be understoodtherefrom.

What I claim as new, and desire to secure by Letters Patent, is:

1. An ester compound of the general formula 0 o-cny oazi (an 0- BY whereY is a group of the class consisting of hydrogen and alkyl groups, and mis one or zero.

2. An ester compound of the general formula 0 OCHY CuHi o- HY where Y isa group 02 the'class consisting of hydrcgen and allryl groups.

3. The'process which comprises mixing phenyl phosphorus oxydichlorldewith a glycol of the formula HO-(CHY),OH, where}! is a group of theclass consisting of hydrogen and alkyl moving substantially all of thehydrogen chloride formed under a vacuum, and then heating to removeresidual ethylene glycol and any residual hydrogen chloride.

5. The process which comprises mixing phenyl phosphorus oxydichloridewith trimethylene glycol, maintaining a temperature not over 25 0.,removing substantially all of the hydrogen chloride formed under avacuum, and then heating to remove residual trimethylene glycol and anyresidual hydrogen chloride.

6. The process which comprises mixing phenyl phosphorus oxydichloridewith 2,3 butanediol, maintaining a temperature not over 25 C., removingsubstantially all of the hydrogen chloride formed under a vacuum, andthen heating to remove-residual butanediol and any residual hydrogenchloride.

'7. The phenylphosphonate of ethylene glycol having the general formula/0 CH: cimix l and a boiling point of approximately 210' C. at 6-7 mm.pressure.

8. The phenvl phosphonate of dimethylethylene glycol having the generalformula 0 ocnom uHr 0 non. and a boiling point of 210-215 C.-at mm.pressure.

9. The phenylphosphonate of trimethylene glycol having the generalformula 0 O-GH:

C Ey CH1 0-0 x and a boiling point of 212-214 C. at 7.5 mm. pressure.

10. The process which comprises mixing phenyl phosphorus oxydichloridewith a glycol of the formula HO(CHY)-0H. where Y is a group DOCK FONTOY.

